dicesium uranyl tetrachloride | 17631-98-0

• 英文名称: dicesium uranyl tetrachloride
• 英文别名: caesium dioxotetrachlorouranate；dicaesium uranyl terachloride
• CAS: 17631-98-0
• 化学式: Cl₄O₂U*2Cs
• 分子量: 677.65
• InChiKey: UDRJJZYJJCICIP-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  -0.48
• 重原子数：
  8.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  dicesium uranyl tetrachloride 以 further solvent(s) 为溶剂， 生成 铀
  参考文献：
  名称：

  对非水介质中锕系元素电化学性质知识的贡献 II：六价铀在各种有机溶剂中的还原

  摘要：

  摘要 六价铀在室温下在各种有机溶剂中以及在六甲基磷酰胺、二甲基砜、环丁砜中在 310 到 400 K 之间的电化学行为已有报道。UO 2 2+ 的还原分两步进行，生成四价铀。取决于溶剂酸度，四价物质可溶或以 UO 2 (cr) 形式沉淀。在所有反应中都证明了许多额外的动力学现象。特别注意以宏观量沉积UO 2 (cr)。

  DOI：

  10.1016/0925-8388(92)90562-n
• 作为产物：
  描述：

  cesium chloride 、 uranyl(VI) acetate dihydrate 在 盐酸 作用下， 以 水 为溶剂， 以25.8%的产率得到dicesium uranyl tetrachloride
  参考文献：
  名称：

  Polarization Dependent High Energy Resolution X-ray Absorption Study of Dicesium Uranyl Tetrachloride

  摘要：

  Dicesium uranyl tetrachloride (Cs2UO2Cl4) has been a model compound for experimental and theoretical studies of electronic structure of U(VI) in the form of UO22+ (uranyl ion) for decades. We have obtained angle-resolved electronic structure information for oriented Cs2UO2Cl4 crystal, specifically relative energies of 5f and 6d valence orbitals probed with extraordinary energy resolution by polarization dependent high energy resolution X-ray absorption near edge structure (PD-HR-XANES) and compare these with predictions from quantum chemical Amsterdam density functional theory (ADF) and ab initio real space multiple-scattering Green's function based FEFF codes. The obtained results have fundamental value but also demonstrate an experimental approach, which offers great potential to benchmark and drive improvement in theoretical calculations of electronic structures of actinide elements.

  DOI：

  10.1021/ic5020016

文献信息

• Equatorial Electronic Structure in the Uranyl Ion: Cs₂UO₂Cl₄ and Cs₂UO₂Br₄
  作者：Dumitru-Claudiu Sergentu、Frédéric Gendron、Eric D. Walter、Sejun Park、Cigdem Capan、R. Gian Surbella、Chuck Z. Soderquist、Gabriel B. Hall、Sergey I. Sinkov、Jochen Autschbach、Herman Cho

  DOI：10.1021/acs.inorgchem.1c02832

  日期：2022.3.7

  in the equatorial plane of the linear UO22+ ion have been measured by nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) experiments and computed by relativistic Kohn–Sham methods with and without environment embedding for Cs2UO2Cl4 and Cs2UO2Br4. This approach expands the possibilities for probing the electronic structure in uranyl complexes beyond the strongly covalent U–O bonds

  已通过核磁共振 (NMR) 和核四极共振 (NQR) 实验测量了线性 UO 2 2+离子赤道平面中的电场梯度 (EFG) 张量，并通过相对论 Kohn-Sham 方法在有和没有环境嵌入的情况下进行了计算对于 Cs 2 UO 2 Cl 4和 Cs 2 UO 2 Br 4。这种方法扩展了探测铀酰配合物中电子结构的可能性，超越了强共价的 U-O 键。综合分析发现卤素位点的两个最大主 EFG 张量分量之一沿 U-X 键 (X = Cl, Br) 指向，第二个与 UO 2平行2+离子；在 Cs 2 UO 2 Cl 4中，分量的大小几乎相等，而在 Cs 2 UO 2 Br 4中，由于溴化物-铯的短程相互作用，赤道分量在一对 Br 位点和轴向分量中占主导地位第二对更大。发现场梯度主轴的方向和相对大小对配体的 σ 和 π 电子捐赠和环境模型敏感。贫235 U 和富 235 U Cs 2 UO 2 Cl 4的Chlorine-35
• Systematic Study of Solid-State U(VI) Photoreactivity: Long-Lived Radicalization and Electron Transfer in Uranyl Tetrachloride
  作者：Jordan A. Herder、Samantha J. Kruse、Aaron D. Nicholas、Tori Z. Forbes、Eric D. Walter、Herman Cho、Christopher L. Cahill

  DOI：10.1021/acs.inorgchem.3c04144

  日期：2024.3.18

  Reported are the syntheses, structural characterizations, and luminescence properties of three novel [UO2Cl4]2– bearing compounds containing substituted 1,1′-dialkyl-4,4′-bipyridinum dications (i.e., viologens). These compounds undergo photoinduced luminescence quenching upon exposure to UV radiation. This reactivity is concurrent with two phenomena: radicalization of the uranyl tetrachloride anion

  报告了三种新型[UO 2 Cl 4 ] 2–化合物的合成、结构表征和发光性质，这些化合物含有取代的1,1'-二烷基-4,4'-联吡啶二阳离子（即紫精）。这些化合物在暴露于紫外线辐射时会发生光致发光猝灭。这种反应性与两种现象同时发生：四氯化铀阴离子的自由基化和光电子转移到紫精，这构成了一个电子从 [UO 2 Cl 4 ] 2–到紫精物质的形式转移。使用电子顺磁共振 (EPR) 光谱阐明了这种行为，并通过一系列表征和计算技术（包括 Rehm-Weller 分析、瞬态密度泛函理论 (TD-DFT) 和态密度 (DOS)）进一步探讨。这项工作对固态铀酰单元的光反应性进行了系统研究，这是基本铀酰化学中未被描述的一个方面。
• Vorobei, M. P.; Bevz, A. S.; Skiba, O. V., Russian Journal of Inorganic Chemistry, 1978, vol. 23, p. 890 - 893
  作者：Vorobei, M. P.、Bevz, A. S.、Skiba, O. V.

  DOI：——

  日期：——
• Leverd, Pascal C.; Berthault, Patrick; Lance, Monique, European Journal of Inorganic Chemistry, 1998, # 12, p. 1859 - 1862
  作者：Leverd, Pascal C.、Berthault, Patrick、Lance, Monique、Nierlich, Martine

  DOI：——

  日期：——
• The resonance Raman effect of dicaesium uranyl tetrachloride in dimethyl sulfoxide
  作者：Takeshi Soga

  DOI：10.1016/s1386-1425(01)00410-3

  日期：2001.8

  The resonance Raman scattering spectra of dicaesium uranyl tetrachloride (Cs2UO2Cl4) in dimethyl sulfoxide ((CH,),SO) have been measured under laser excitation of the uranyl ion in resonance with the (1)Sigma (+)(g) --> (1)phi (g) Laport-forbidden f-f electronic transitions (520-450 nm) by using 10 output lines of the argon-ion laser at room temperature. The excitation profile of the totally symmetric stretching vibrational mode of uranyl observed at 830 cm(-1) is presented and analyzed in terms of the transform methods which are able to formally bypass multimode complexities. The non-Condon model (generalized B, C-terms of scattering) gives a relatively good agreement with the resonance excitation profile of experiment. Reliable value of the nuclear displacement on going the (1)Sigma (+)(g) --> (1)phi (g) electronic transition and the amount of charge transferred from the ligand to uranium of uranyl ion both in the ground and excited states are obtained. It is found that the average number of ligands coordinated equatorically to the central uranium atom affects on the amount of charge transferred from the ligand to uranium, especially in the electronic excited state. As increasing the average number of ligands, the amount of charge transferred from the ligand to uranium increases in the ground state, while in the electronic excited state, the charge transferred decreases. (C) 2001 Elsevier Science B.V. All rights reserved.